This invention relates to production of oxygenate enhanced C.sub.5 + olefinic gasoline by conversion of the isoalkene (branched olefin) components of gasoline to high octane value alkyl tertiary-alkyl ethers. The invention particularly relates to an etherification process for production of tertiary alkyl ethers employing a noble metal modified regenerable acidic zeolite catalyst concurrently with cofed hydrogen. The combination of zeolite catalyst modification and hydrogen cofeeding in the etherification step results in a highly advantageous decrease in the rate of catalyst deactivation while enhancing the octane value of the gasoline.
It is known that isobutylene and isoamylenes, and other isoalkenes or iso-olefins, produced by hydrocarbon cracking may be reacted with methanol and other C.sub.1 -C.sub.4 lower aliphatic alcohols, or alkanol, over an acidic catalyst to provide methyl tertiary butyl ether (MTBE) or the like. Generally, it is known that asymmetrical ethers having the formula (CH.sub.3).sub.3 C--O--R, where R is a C.sub.1 -C.sub.4 alkyl radical, are particularly useful as octane improves for liquid fuels, especially gasoline.
MTBE, ethyl t-butyl ether (ETBE), tert-amyl methyl ether (TAME) and isopropyl t-butyl ether (IPTBE) are known to be high octane ethers. The liquid phase reaction of methanol with isobutylene and isoamylenes at moderate conditions with a resin catalyst is well known. Suitable resin catalysts are polymeric sulfonic acid exchange resin such as Amberlyst 15 and zeolites such as zeolite Beta and ZSM-5. The acid resin catalysts are effective catalysts at temperatures below 90.degree. C. At higher temperatures the resin catalyst is unstable. Typically, with acid resin catalyst the etherification reaction is carried out in liquid phase. However, mixed phase etherification is known, particularly where the catalyst is contained as a fixed bed in a fractionator which services to both separate the reaction products and operate as a vessel to contain the catalyst under etherification conditions. U.S. Pat. No. 4,978,807 to (Smith) describes an etherification catalyst reaction zone contained within a distillation tower.
Typical hydrocarbon feedstock materials for etherification reactions include olefinic streams, such as cracking process light gas containing butane isomers in mixture with substantial amounts of paraffins including n-butane and isobutane. The C.sub.4 components usually contain a major amount of unsaturated compounds, such as 10-40% isobutylene, 20-55% linear butenes, and small amounts of butadiene. Also, C.sub.4 + heavier olefinic hydrocarbon streams may be used, particularly mixtures of isobutylene and isoamylene. C.sub.5 + olefinic hydrocarbon streams containing isoamylene comprising fluid catalytic cracking (FCC) gasoline are an especially important feedstock.
Improvements in the etherification of isoamylenes to TAME in C.sub.5 + FCC gasoline are very desirable to meet the amended requirements of the Clean Air Act with respect to gasoline oxygen content while avoiding C.sub.4 - hydrocarbon evaporative emissions. These amendments specify that gasoline sold in CO nonattainment areas during winter months will have 2.7 wt. % oxygen by 1992 while in ozone nonattainment areas 2.0 wt. % year round must be achieved by 1995.
As noted above, the use of zeolite catalyst for the etherification reaction of lower alkanol with isoolefins to produce MTBE and/or TAME is well known in the art. Among the advantages in employing acidic zeolite for the catalysis of etherification is the fact that it is much more readily regenerable than acidic resin catalyst. While sulfonated resin catalyst such as Amberlyst-15 are highly effective as etherification catalysts the fact that they are organic resins limits the temperatures to which they can be exposed without degradation. Zeolites, on the other hand, are stable at high temperatures which allows the repeated regeneration of deactivated catalyst. High temperature catalyst regeneration is by far the preferred route for regeneration to remove carbonaceous deposits, particularly produced by diene contaminates in the etherification hydrocarbon feedstream.
U.S. Pat. No. 4,605,787 to Chu et al., incorporated herein by reference, describes a process for the preparation of methyl tertiary butyl ether which comprises reacting isobutylene and methanol in the vapor phase in the presence of zeolite catalyst. Under the conditions described for the vapor phase etherification, side reactions, particularly the dimerization of isobutylene, are virtually eliminated.
European Patent application 0055045 to Daniel also teaches a process for the production of methyl tertiary butyl ether employing zeolite catalyst such as zeolite beta which may contain noble metals.
U.S. Pat. No. 4,330,679 to Kohler describes a process for the preparation of alkyl tertiary alkyl ethers using catalyst acidic resin which may contain a metal of subgroups VI, VIII, or VII of the Periodic Table. The catalyst employed is effective in etherification without noticeable oligomerization of the olefin.
A process has been discovered for the production of alkyl tertiary-alkyl ether from C.sub.4 -C.sub.5 + hydrocarbons with a reduced rate of catalyst deactivation and a consequent increase in cycle length before regeneration is required.
It is an object of the present invention to provide a process for the production of C.sub.5 + gasoline rich in TAME employing a process and catalyst system which substantially reduces the rate of catalyst deactivation caused by the presence of dienes in the etherification feedstock.
Yet another object of the present invention is to provide a process for extending the effective life of zeolite catalyst in the production of alkyl tertiary alkyl ethers by incorporating noble metals in the catalyst and cofeeding hydrogen during the etherification reaction.
It has been discovered that the process of the invention results in an advantageous isomerization of monoolefins, especially alpha olefins, in the feedstream to produce more useful internal olefins.
More particularly, a process for the production of high octane value alkyl tertiary alkyl ether with a reduced rate of catalyst deactivation has been discovered which comprises contacting a feedstream comprising C.sub.4 + hydrocarbons rich in isoolefins and containing dienes and/or heteroatoms, an alkanol feedstream and a cofed hydrogen feedstream with regenerable, acidic metallosilicate catalyst particles, preferably aluminosilicate, containing a metal selected from Group VIIIA of the Periodic Table of the Elements, in an etherification zone under etherification conditions. An effluent stream is produced containing alkyl tertiary alkyl ether, unconverted isoolefin and unconverted alkanol; and the rate of catalyst deactivation is reduced.
In a preferred embodiment the feedstream comprises C.sub.5 + hydrocarbons rich in isoolefins and containing dienes and/or alpha olefins, an alkanol feedstream and a cofed hydrogen feedstream, whereby gasoline rich in TAME is produced.